Certain geranyl ethers

ABSTRACT

COMPOUNDS HAVING THE FORMULA   R2-C6H4-O-CH2-CH=C(-R1)-(CH2)2-CH&lt;(-(O)N-C(-CH3)(-R)-)   IN WHICH R AND R1 ARE INDEPENDENTLY METHYL OR ETHYL; N IS THE INTEGER ZERO TO ONE; R2 IS CERTAIN HETEROCYCLIC RADICALS; THE USE OF THESE COMPOUNDS IN CONTROLLING INSECTS.

United States Patent Oflice Patented Oct. 16, 1973 3,766,208 CERTAIN GERANYL ETHERS Hwalin Lee, San Francisco, Ferenc M. Pallos, Pleasant Hill, and Julius J. Menn, Saratoga, Calif., assignors to Staufier Chemical Company, New York, N.Y.

No Drawing. Application Mar. 29, 1971, Ser. No. 129,192,

now Patent No. 3,701,759, which is a continuation-inpart of application Ser. No. 856,140, Sept. 8, 1969, which in turn is a continuation-in-part of application Ser. No. 815,229, Apr. 10, 1969, both now abandoned. Divided and this application Aug. 21, 1972, Ser. No. 282,647

Int. Cl. A61k 27/00; C07d 13/04, 71/00 US. Cl. 260327 M 1 Claim ABSTRACT OF THE DISCLOSURE Compounds having the formula in which R and R are independently methyl or ethyl; n is the integer zero to one; R is certain heterocyclic radicals; the use of these compounds in controlling insects.

This application is a division of application Ser. No. 129,192, now US. Pat. No. 3,701,759, patented Oct. 31, 1972, filed Mar. 29, 1971, which is in turn a continuationin-part of application Ser. No. 856,140, filed Sept. 8, 1969, now abandoned, which is a continuation-in-part of application Ser. No. 815,229, filed Apr. 10, 1969, now abandoned.

This invention relates to the use of certain novel chemical compounds in controlling insects, more particularly, the chemical compounds are certain phenyl geranyl ethers and their expoxides.

It has been found that there is a class of compounds which acts in a different manner on insects than presently used insecticides and exerts a disrupting influence upon the normal development of insects. Such compounds impede the metamorphosis of the normal pupation of pest insects and result in the formation of members of the treated species which are non-viable or sterile. This ultimately leads, indirectly at least, to the destruction of a pest population.

The compounds of the present invention are believed to have the further advantages that they are non-toxic to warm-blooded animals and highly effective to control insects at low dosages. It is also hoped that it will be more difficult for insects to develop resistance against these compounds.

One embodiment of the present invention is concerned with novel pesticidal compositions.

In another embodiment, the invention is concerned with the active pesticidal component of such compositions.

In still another embodiment, the invention is concerned with a process for controlling insects by hindering or impeding the metamorphosis and reproduction of the insects.

The compounds of the present invention that are useful in controlling insects are those having the formula in which R and R are independently methyl or ethyl, n is the integer zero or 1, preferably 1; R is the heterocyclic group CHR -X GNP.-

cHR -X in which X or X is oxygen or sulfur, and R R or R is hydrogen, methyl or ethyl; most preferably R is in the para position.

Carbon atoms, joined to two or less hydrogen atoms, occupy each angle in the backbone of the compound represented by the above formula. Letters at the terminals and branches have been used to show the attached groups.

As indicated heretofore, the above compounds are useful in impeding the metamorphosis and/or the repro duction of insects. The activity of the compounds is such that insects at any stage of their development can be effectively treated therewith.

The compound having the formula in which R, R and R are as defined can be prepared by the following reaction:

in which R, R and R are as defined, and X is chlorine or bromine, or iodine.

Preferably, Reaction No. l is carried out in a solvent such as 1,2-dimethoxyethane, with stirring by slowly adding an acid acceptor, such as a diluted solution of alcoholic KOH, at room temperature, followed by heating at reflux to complete the reaction. The reaction product is recovered by conventional techniques such as stripping off the solvent in vacuum, extracting the residue with ether, washing the ether phase with 10% KOH solution and then with water, followed by drying with anhydrous MgSO Finally, the drying agent is filtered off and the ether is removed by vacuum stripping.

Preferably, Reaction No. 1 is carried out using equal mole amounts of the reactant, although an excess of either reactant can be used.

Compounds having the formula Rzg/ w/ in which R and R are as defined and R is as defined, excluding said heterocyclic group when containing a sulfur atom can be prepared by the following reaction epoxidizing agent in which R and R are as defined and R is said heterocyclic group when it contains a sulfur atom, and can be prepared by the following reactions:

X CH8 epoxldtzlng in which R and R are as defined, and X is chlorine or bromine, or iodine, and

in which R and R are as defined and R is said heterocyclic group when it contains a sulfur atom, and X is chlorine or bromine, or iodine.

Preferably, Reaction Nos. 3 and 4 are carried out under the same conditions as described for Reaction Nos. 2 and 1, respectively.

A method of preparation for the compounds where either R and R are ethyl and was published by W. S. Bowers, Gordon Research Conf., June 1968, in a symposium entitled, Bio-Chemistry and Agriculture, Tilton, N.H.

Preparation of the compounds of this invention is illustrated by the following examples.

Example I Example II 2- (4-hydroxy) phenyl-1,3-dithiolane CHr- S CH- OH CH S 36.6 gr. (0.3 mole) p-hydroxybenzaldehyde, 30.0 gr. (0.32 mole) 1,2-ethanedithiol, 1.0 gr. Z-naphthalene sulfonic acid and 600 ml. benzene are mixed together and azeotropically distilled. After 1 hour 5.5 ml. water is collected. The reaction product is crystallized by cooling and 42.3 gr. of solid product is separated by filtration, M.P.: 110-113 C. The solid product is recrystallized from 300 ml. hot benzene and filtered to yield 31.9 gr. of the desired product, M.P.: 112-114 C.

Example III on on,

2.2 gr. (0.011 mole) of the product of Example II, 2.2 ml. 1,?rdimethoxyethane and 2.3 gr. of the product of Example I are mixed together. 11.0 ml. (1.0 mole) KOH in EtOH is added dropwise. The mixture is stirred at room temperature for 2 hours. 30 ml. ether is added and the mixture transferred into a separatory funnel. The mixture is washed twice with 10% Na CO solution and once with water, then dried over anhydrous MgSO It is then filtered and stripped to yield 3.1 gr. of a compound corresponding to the above formula, n =l.5770. The structure is confirmed by IR and NMR spectroscopy.

INSECTICIDAL EVALUATION TEST The degree of activity of a candidate compound to hinder or impede the metamorphosis of insects is measured by treating the penultimate larval stage of a representative insect with the compound and examining it after its last molt toward the adult form for retention of immature features.

Specifically, yellow mealworm, Tenebrio molitor, L. larvae are maintained at 28 C. and 40% humidity on a diet of bran flakes. Prepupae are collected from the culture and kept in separate containers. The pupae collected once daily are 1-25 hours old at the time of treatment. By means of a syringe, suitable amounts of candidate compounds in 0.5 or 1.0 1. of acetone are applied to the venter of Tenebrio molitor, L. pupae. Treated pupae are maintained at 28 C. and 40% humidity until the adults emerged (usually within 6-8 days). Emerged adults are graded as positive, negative, or dead. To be considered a positive response, the presence of typical pupal cuticle, urogomphi, gin trap, and abnormal wings, etc. are required. For each test, 2 groups of 20 pupae were used and the averaged results were reported.

The dose of a candidate compound per pupa that is needed to kill or give a positive response in the above insecticidal evaluation test for 10 of the 20 pupae is determined, i.e., the ED is determined.

For the compound of Example III, a test result of 0.08 g. was observed.

The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, dusts, and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, Xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifiuoromethane, etc. If desired, however, the active compounds can be applied directly to feedstutls, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition, for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

6 What is claimed: 1. A compound of the formula:

in which X or X is oxygen or sulfur, and R R or R is hydrogen, methyl or ethyl.

References Cited UNITED STATES PATENTS 3,701,759 10/1972 Lee et al. 260-240 H HENRY R. JILES, Primary Examiner C. M. S. I AISLE, Assistant Examiner U.S. Cl. X.R. 

